EP0619803B1 - Verfahren zur herstellung von adipinsäure - Google Patents
Verfahren zur herstellung von adipinsäure Download PDFInfo
- Publication number
- EP0619803B1 EP0619803B1 EP92925455A EP92925455A EP0619803B1 EP 0619803 B1 EP0619803 B1 EP 0619803B1 EP 92925455 A EP92925455 A EP 92925455A EP 92925455 A EP92925455 A EP 92925455A EP 0619803 B1 EP0619803 B1 EP 0619803B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iridium
- iodide
- pentenoic
- acid
- aliphatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000001361 adipic acid Substances 0.000 title claims abstract description 23
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 39
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 38
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 27
- YIYBQIKDCADOSF-UHFFFAOYSA-N pentenoic acid group Chemical group C(C=CCC)(=O)O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims description 17
- -1 pentenoic compound Chemical class 0.000 claims description 14
- 239000000203 mixture Chemical class 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 150000001559 benzoic acids Chemical class 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 9
- 229910052703 rhodium Inorganic materials 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical compound [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010960 commercial process Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004989 dicarbonyl group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 description 1
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 description 1
- LMHCYRULPLGEEZ-UHFFFAOYSA-N 1-iodoheptane Chemical compound CCCCCCCI LMHCYRULPLGEEZ-UHFFFAOYSA-N 0.000 description 1
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical compound OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 description 1
- RVHOBHMAPRVOLO-UHFFFAOYSA-N 2-ethylbutanedioic acid Chemical compound CCC(C(O)=O)CC(O)=O RVHOBHMAPRVOLO-UHFFFAOYSA-N 0.000 description 1
- IQRUSQUYPCHEKN-UHFFFAOYSA-N 2-iodobutane Chemical compound CCC(C)I IQRUSQUYPCHEKN-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical class CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- AZFHXIBNMPIGOD-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one iridium Chemical compound [Ir].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O AZFHXIBNMPIGOD-UHFFFAOYSA-N 0.000 description 1
- FLPVVTDEKLGZDZ-UHFFFAOYSA-N 4-iodobutyl acetate Chemical compound CC(=O)OCCCCI FLPVVTDEKLGZDZ-UHFFFAOYSA-N 0.000 description 1
- HYFUIKONZIAHFT-UHFFFAOYSA-N 5-(bromomethyl)-1h-imidazole Chemical compound BrCC1=CNC=N1 HYFUIKONZIAHFT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical class [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
- LEKJTGQWLAUGQA-UHFFFAOYSA-N acetyl iodide Chemical compound CC(I)=O LEKJTGQWLAUGQA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- XWDKRVSSHIJNJP-UHFFFAOYSA-N carbon monoxide;iridium Chemical group [Ir].[Ir].[Ir].[Ir].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] XWDKRVSSHIJNJP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- OYNRRNCNOGYBQB-UHFFFAOYSA-N ethyl hexanoate iridium(3+) Chemical compound [Ir+3].CCCCCC(=O)OCC OYNRRNCNOGYBQB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- NSTASKGZCMXIET-UHFFFAOYSA-N iridium(iv) oxide Chemical compound [O-2].[O-2].[Ir+4] NSTASKGZCMXIET-UHFFFAOYSA-N 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KJALUUCEMMPKAC-ONEGZZNKSA-N methyl (e)-pent-3-enoate Chemical compound COC(=O)C\C=C\C KJALUUCEMMPKAC-ONEGZZNKSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
Definitions
- This invention relates to a process for the manufacture of adipic acid.
- adipic acid The dominant commercial process for the manufacture of adipic acid involves the air-oxidation of cyclohexane to form a mixture of cyclohexanol and cyclohexanone, which is subsequently oxidized with nitric acid to form a mixture of carboxylic acids, including adipic acid.
- Another patented process for making adipic acid involves the hydrocarboxylation of pentenoic acids and their esters.
- Pentenoic acids and their esters, and in particular 3-pentenoic acid are available from butadiene and butadiene derived feedstocks by metal catalyzed hydrocarboxylation.
- Such processes have the potential of providing high yield, high rate, low pollution processes for the manufacture of adipic acid.
- Burke discloses in U.S. 4,939,298, that branched diacids can be isomerized to adipic acid by heating in the presence of carbon monoxide and an iodide or bromide promoted rhodium catalyst.
- valerolactone gamma-valerolactone
- Valerolactone can be hydrocarboxylated to adipic acid as described in Burke EPO published application 0395038, but there are costs and yield losses associated with such processes.
- Craddock et al. (U.S. 3,816,489) have disclosed a process for the production of terminal carboxylic acids from ethylenically unsaturated compounds by hydrocarboxylation "in the presence of catalyst compositions essentially comprising iridium compounds and complexes, together with an iodide promoter in critical proportions".
- U.S. 3,816,488 discloses that similar results can be obtained using rhodium catalysts.
- the preferred reaction solvents are monocarboxylic acids having 2 to 20 carbon atoms.
- Gosselin et al. describe a process for the preparation of adipic acid from at least one pentenoic acid by hydrocarboxylation in the presence of a iodide promoted iridium catalyst in conjunction with a carboxylic acid solvent selected from saturated aliphatic carboxylic acids, ethylenic aliphatic carboxylic acids and aromatic acids, having less than 20 carbon atoms, the atomic ratio I/Ir being less than 10.
- the catalyst used is a iodide promoted rhodium catalyst in conjunction with a co-catalyst which may be a source of iridium.
- the process of this invention seeks to overcome the disadvantages of the prior art by providing a high yield, high rate, low-pollution process for the manufacture of adipic acid from esters of pentenoic acids.
- the process of this invention gives high linear selectivity while avoiding the use of halocarbon solvents and results in the formation of relatively low levels of valerolactone.
- This invention provides a process for the production of adipic acid which comprises forming a reaction mixture comprising (a) at least one pentenoic compound selected from the group consisting of a methyl ester of a pentenoic acid, and an ethyl ester of a pentenoic acid, (b) carbon monoxide, (c) at least about a stoichiometric amount of water, based on the pentenoic compound, (d) a carboxylic acid solvent selected from aliphatic C 2 -C 20 monocarboxylic acids, aliphatic C 4 -C 20 dicarboxylic acids, benzoic acid and substituted benzoic acids and mixtures thereof, and (e) an iridium-containing catalyst and an iodide compound that are both soluble in the combination of other components, the concentration of iridium being about 100 to 5,000 parts per million of the reaction mixture, the concentration of iodide being about 500 to 8,000 parts per million of the reaction mixture, and the m
- This invention provides an efficient, low, pollution route to adipic acid based on the hydrogen iodide promoted, iridium catalyzed hydrocarboxylation of selected pentenoic compounds.
- hydrocarboxylation of 3-pentenoic acid it has been found that the use of iridium catalysts provides higher reaction rates, higher yields of adipic acid at high conversion of the starting material, and high product linearity in carboxylic acid solvents. In a continuous commercial process higher one pass yields and higher overall yields of adipic acid will result in higher productivity.
- One critical feature of this process is the use of relatively low molar ratios of iodide promoter to iridium in order to maintain high selectivity to linear products while minimizing the production of valerolactone and saturated by-products. Because of the corrosivity of iodide, the use of lower amounts of iodide is an advantage in itself. Another crucial feature of this process is its suitability for use in conjunction with carboxylic acid solvents. The use of carboxylic acid solvents not only simplifies processing, but eliminates the need for the handling and containment of hazardous halocarbon solvents.
- Suitable substrates for the process of this invention include the esters of 2-pentenoic acid, 3-pentenoic acid and 4-pentenoic acid.
- esters which can be employed in the process of this invention include methyl and ethyl esters.
- Feedstocks which consist primarily of esters of 3-pentenoic acid are preferred for reasons of cost and availability.
- Anhydrides of pentenoic acids may also be beneficially employed in the process of this invention as long as sufficient water for both the hydrolysis of the anhydride and the hydrocarboxylation is present.
- the product may contain adipic acid monoester which can be hydrolyzed in situ or in a subsequent step to give adipic acid.
- the initial concentration of the pentenoic compound will be between 5 and 50% by weight of the reaction mixture in a batch process, and between 5 and 50% by weight of the feed in a continuous process.
- the loading of the pentenoic compound is between 10 and 30% by weight.
- the iridium catalyst can be provided from any source or by any material which will produce iridium ions under hydrocarboxylation conditions, i.e. iridium materials that are soluble in the other components of the reaction mixture.
- iridium materials that are soluble in the other components of the reaction mixture.
- the materials which can be employed as the source of the iridium are iridium metal, iridium salts, iridium oxides, iridium carbonyl compounds, organoiridium compounds, coordination compounds of iridium and mixtures thereof.
- Such compounds include, but are not limited to, iridium(III) chloride and its hydrates, iridium(III) bromide and its hydrates, iridium(III) iodide, iridium(III) oxide, iridium(IV) oxide, iridium(III) acetylacetonate, iridium(I) dicarbonyl acetylacetonate, iridium (III) nitrate, iridium(III) ethylhexanoate and dodecacarbonyl tetrairidium.
- Preferred sources of iridium catalyst include iridium(III) chloride and its hydrates, iridium(III) iodide, and iridium(I) dicarbonyl acetylacetonate.
- Suitable concentrations of iridium are in the range of 100 ppm to 5000 ppm (parts per million) based on the weight of the reaction mixture although higher levels may be employed.
- the concentration of iridium is in the range of 400 ppm to 4000 ppm, more preferably 800 ppm to 2000 ppm.
- the iridium catalyst which can be preformed or formed in situ, must be promoted by a source of iodide that is soluble in the other components of the reaction mixture in order to achieve satisfactory results.
- concentration of iodide promoter below about 8,000 ppm total iodide based on the weight of the reaction mixture
- the absolute level of iodide is not as critical as the molar ratio of iodide to iridium.
- Iodide to iridium ratios between 1 and 5 may be beneficially employed in the process of this invention. Iodide to iridium ratios between 1 and 3 are preferred and ratios between 2 and 3 are most preferred.
- iodide to iridium ratios greater than 3:1 are employed, it is advantageous to employ lower iridium concentrations. This serves to reduce the total concentration of free hydrogen iodide and thus reduce the overall corrosivity of the reaction mixture.
- valerolactone formed in this process is dependent on a number of factors, high free hydrogen iodide concentration tends to increase the amount of valerolactone formed.
- iodide to iridium ratios of less than 21: are employed, it is believed that, in order to optimize the catalytic activity of the iridium, other ligands should be present in sufficient amounts to fill the iridium coordination sphere. Examples of such ligands are chloride and bromide.
- the iodide promoter can be provided by hydrogen iodide, iodine, alkali metal iodides, alkaline earth metal iodides, organic iodides, or any other source which will provide hydrogen iodide under hydrocarboxylation conditions.
- Preferred sources of iodide include hydrogen iodide, aqueous solutions of hydrogen iodide, acetyl iodide, 4-iodobutyl acetate, aryl iodides, C 1 -C 10 alkyl iodides, such as methyl iodide, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1,4-diiodobutane, and iodoheptane.
- the iodide and iridium can be present in the same compound, e.g., as in iridium(III) iodide.
- the most preferred sources of iodide promoter are hydrogen iodide, aqueous hydrogen iodide, methyl iodide and iodobutanes.
- the concentration of water at the start of the hydrocarboxylation reaction should be no more than about 15% by weight of the total reaction mixture. In order to obtain higher reaction rates and better product linearity it is preferred that the concentration of water at the start of the hydrocarboxylation reaction be no more than about 10% by weight.
- Reaction temperatures in the range of 100° to 220°C may be employed in the practice of this invention. However, at lower temperatures the reaction rates are slower and the linear selectivity is somewhat less, while at temperatures above 220° C significant decomposition of the product adipic acid can occur. In general, temperatures in the range of 130° to 220°C are satisfactory, while 170° to 210°C are preferred. Optimum reaction temperatures will vary depending on the nature of the solvent system employed.
- Suitable carboxylic acid solvents for the process of this invention include, but are not limited to, aliphatic C 2 -C 20 monocarboxylic acids, aliphatic C 4 -C 20 dicarboxylic acids, benzoic acid, and alkyl substituted benzoic acids.
- Preferred solvents are aliphatic C 2 -C 20 monocarboxylic acids and aliphatic C 5 -C 8 dicarboxylic acids. Mixtures of the monocarboxylic and dicarboxylic acids produced in the process of this invention are particularly useful as solvents for the process of this invention.
- Such mixtures contain valeric acid, methylbutyric acids, adipic acid, 2-methylglutaric acid, ethylsuccinic acid, and dimethyl-succinic acid as well as other components such as valerolactones.
- Solvent usually is present in the reaction mixture in the amount of about 40 to 94 percent by weight of the reaction mixture. It is often most convenient to use about 65 to 90 percent by weight of the initial reaction mixture.
- hydrocarbon solvents may be beneficially employed in the iridium catalyzed hydrocarboxylation process of the present invention to produce dibasic acids with high selectivity for adipic acid.
- Hydrocarbon solvents may also be employed as co-solvents or diluents in conjunction with carboxylic acid solvents. Advantages associated with the use of a co-solvent or diluent include enhanced recovery of adipic acid and improved mobility of the process streams.
- hydrocarbon solvents which may be employed include, but are not limited to, cyclohexane, benzene, toluene and xylenes.
- pentenoic acids and their esters are most readily prepared from butadiene and butadiene derived feedstocks by metal catalyzed hydrocarboxylation.
- metals such as rhodium, which catalyze the hydrocarboxylation of butadiene and butadiene derived feedstocks are compatible with the process of this invention.
- the reaction mixtures obtained from the rhodium catalyzed hydrocarboxylation of butadiene and butadiene derived feedstocks can be used directly in the process of this invention without the need to remove the rhodium catalyst.
- linear selectivity can be controlled by adjusting the ratio of iridium to rhodium. Generally, a molar ratio of iridium to rhodium of greater than about 2 to 1 is preferred.
- the process of this invention is illustrated by the following example.
- the experiment was carried out in a 300 ml Hastelloy autoclave.
- the products were characterized by first esterifying the carboxylic acid components (by treatment with boron trifluoride in methanol at 90°C for one hour), diluting with water, and then analyzing a methylene chloride extract by capillary gas chromatography using orthodichlorobenzene as the internal standard.
- the results, which were converted to moles and then normalized to 100%, are presented in Table 1.
- the time given in Table 1 represents the time from the completion of the addition of the pentenoic acid or ester.
- the autoclave was charged with 130 grams acetic acid as solvent, 0.233 grams of iridium trichloride, 0.5 grams 57% HI, and 0.5 grams water to give a solution in which the molar ratio of iodide to iridium was 2.9:1.
- the autoclave was purged with CO to remove traces of air, and then heated at 170° C under about 4685 kPa (680 psig) CO for 2 hours. The temperature was then increased to 190oC and the pressure was adjusted to about 4823 kPa (700 psig) prior to the injection of a mixture of 20 grams of trans methyl 3-pentenoate, 3.5 grams water, and 5 grams of acetic acid in 5 equal portions at 10 minute intervals.
- the calculated iridium concentration after the addition was about 939 ppm.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Claims (7)
- Verfahren zur Herstellung von Adipinsäure, welches umfaßt Bilden eines Reaktionsgemisches, welches umfaßt (a) wenigstens eine Pentenverbindung, ausgewählt aus der Gruppe, bestehend aus einem Methylester einer Pentensäure und einem Ethylester einer Pentensäure, (b) Kohlenmonoxid, (c) wenigstens etwa eine stöchiometrische Menge Wasser, bezogen auf die Pentenverbindung, (d) ein Carbonsäure-Lösungsmittel, ausgewählt aus aliphatischen C2-C20-Monocarbonsäuren, aliphatischen C4-C20-Dicarbonsäuren, Benzoesäure und substituierter Benzoesäure und Gemischen davon, und (e) einem Iridiumhaltigen Katalysator und einer Iodidverbindung, die beide löslich sind in der Kombination der anderen Komponenten, wobei die Konzentration an Iridium 100 bis 5000 Teile auf 1 Million Teile des Reaktionsgemisches beträgt, die Konzentration an Iodid 500 bis 8 000 Teile auf 1 Million Teile des Reaktionsgemisches beträgt, und das Molverhältnis von Iodid zu Iridium 1:1 bis 5:1 beträgt, und Umsetzen dieses Gemisches bei einer Temperatur im Bereich von 100 bis 220 °C und bei einem Druck im Bereich von 0 bis 13280 kPa (0 bis 2000 psig).
- Verfahren nach Anspruch 1, bei dem die Temperatur zwischen 170 ° und 210 °C liegt und die Iridiumkonzentration zwischen 800 und 2 000 ppm liegt.
- Verfahren nach Anspruch 2, bei dem das Molverhältnis von Iodid zu Iridium 1:1 bis 3:1 beträgt.
- Verfahren nach Anspruch 1, bei dem das Lösungsmittel ein Gemisch der bei dem Verfahren hergestellten Mono- und Dicarbonsäuren ist.
- Verfahren nach Anspruch 4, bei dem das Molverhältnis von Iodid zu Iridium 2:1 bis 3:1 beträgt.
- Verfahren nach Anspruch 1, bei dem ein Kohlenwasserstoff-Colösungsmittel eingesetzt wird.
- Verfahren nach Anspruch 1, bei dem das Lösungsmittel ausgewählt wird aus aliphatischen C2-C20-Monocarbonsäuren und aliphatischen C5-C8-Dicarbonsäuren und aus Gemischen davon.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US804559 | 1985-12-04 | ||
US80455991A | 1991-12-10 | 1991-12-10 | |
US07/944,997 US5218144A (en) | 1991-12-10 | 1992-09-15 | Process for the manufacture of adipic acid |
US944997 | 1992-09-15 | ||
PCT/US1992/010279 WO1993012063A1 (en) | 1991-12-10 | 1992-12-03 | Process for the manufacture of adipic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0619803A1 EP0619803A1 (de) | 1994-10-19 |
EP0619803B1 true EP0619803B1 (de) | 1997-01-15 |
Family
ID=27122705
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92925455A Expired - Lifetime EP0619803B1 (de) | 1991-12-10 | 1992-12-03 | Verfahren zur herstellung von adipinsäure |
Country Status (7)
Country | Link |
---|---|
US (1) | US5218144A (de) |
EP (1) | EP0619803B1 (de) |
JP (1) | JPH07500346A (de) |
CA (1) | CA2117323A1 (de) |
DE (1) | DE69216856T2 (de) |
ES (1) | ES2096111T3 (de) |
WO (1) | WO1993012063A1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2714306B1 (fr) * | 1993-12-29 | 1996-09-27 | Rhone Poulenc Chimie | Procédé de préparation d'une solution à base d'iridium et son utilisation en tant que catalyseur. |
US5292944A (en) * | 1993-06-29 | 1994-03-08 | E. I. Du Pont De Nemours And Company | Process for the preparation of adipic acid or pentenoic acid |
FR2749582B1 (fr) * | 1996-06-07 | 1998-07-17 | Rhone Poulenc Fibres | Procede d'hydroxycarbonylation des acides pentenoiques |
US5710325A (en) * | 1996-11-01 | 1998-01-20 | E. I. Du Pont De Nemours And Company | Manufacture of adipic acid |
US5883265A (en) * | 1997-04-15 | 1999-03-16 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactones and/or hydrates and/or esters thereof |
US6184391B1 (en) | 1997-04-15 | 2001-02-06 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactones and/or hydrates and/or esters thereof |
US6235932B1 (en) | 1999-06-18 | 2001-05-22 | Chemintel (India) Private Ltd. | Process for preparation of adipic acid |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816489A (en) * | 1968-08-15 | 1974-06-11 | Monsanto Co | Increasing the selectivity and yield in the production of carboxylic acids |
US3579551A (en) * | 1968-08-15 | 1971-05-18 | Monsanto Co | Production of carboxylic acids |
JPS5551037A (en) * | 1978-10-11 | 1980-04-14 | Noguchi Kenkyusho | Preparation of dicarboxylic acid by carbonylation reaction of lactones |
US4334092A (en) * | 1980-06-30 | 1982-06-08 | Texaco Inc. | Method of preparing aliphatic carboxylic acids |
US4659518A (en) * | 1980-12-24 | 1987-04-21 | The Halcon Sd Group, Inc. | Preparation of carboxylic acids |
US4640802A (en) * | 1981-12-10 | 1987-02-03 | Shell Oil Company | Process for the co-production of carboxylic acids and carboxylic acid esters |
US4612387A (en) * | 1982-01-04 | 1986-09-16 | Air Products And Chemicals, Inc. | Production of carboxylic acids and esters |
US4622423A (en) * | 1984-11-09 | 1986-11-11 | E. I. Du Pont De Nemours And Company | Hydrocarboxylation of butadiene to 3-pentenoic acid |
US4788333A (en) * | 1985-01-07 | 1988-11-29 | E. I. Du Pont De Nemours And Company | Hydrocarboxylation of unsaturated carboxylic acids to linear dicarboxylic acids |
US4780334A (en) * | 1987-03-13 | 1988-10-25 | General Electric Company | Method and composition for depositing silicon dioxide layers |
US4939298A (en) * | 1988-12-12 | 1990-07-03 | E. I. Du Pont De Nemours And Company | Isomerization of carboxylic acids |
FR2666808B1 (fr) * | 1990-09-18 | 1994-04-01 | Rhone Poulenc Chimie | Procede de preparation de l'acide adipique par hydrocarboxylation d'acides penteniques. |
FR2675797B1 (fr) * | 1991-04-26 | 1994-10-28 | Rhone Poulenc Chimie | Procede de preparation de l'acide adipique par hydrocarboxylation d'acides penteniques. |
-
1992
- 1992-09-15 US US07/944,997 patent/US5218144A/en not_active Expired - Fee Related
- 1992-12-03 JP JP5510941A patent/JPH07500346A/ja active Pending
- 1992-12-03 ES ES92925455T patent/ES2096111T3/es not_active Expired - Lifetime
- 1992-12-03 WO PCT/US1992/010279 patent/WO1993012063A1/en active IP Right Grant
- 1992-12-03 DE DE69216856T patent/DE69216856T2/de not_active Expired - Fee Related
- 1992-12-03 CA CA002117323A patent/CA2117323A1/en not_active Abandoned
- 1992-12-03 EP EP92925455A patent/EP0619803B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0619803A1 (de) | 1994-10-19 |
DE69216856T2 (de) | 1997-07-10 |
DE69216856D1 (de) | 1997-02-27 |
WO1993012063A1 (en) | 1993-06-24 |
ES2096111T3 (es) | 1997-03-01 |
CA2117323A1 (en) | 1993-06-24 |
JPH07500346A (ja) | 1995-01-12 |
US5218144A (en) | 1993-06-08 |
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